Soil micronutrient product

ABSTRACT

A soil micronutrient product prepared from petroleum coke by oxidizing said coke with oxygen in the presence of water followed by contacting with a metal or ammonium containing cation solution to produce a family of cation exchanged derivatives of oxidized coke. The products of the invention may be used as a plant mulch, a soil conditioner, a source of carbon and trace elements for soil micro-organisms, petroleum catalyst and as a low cost ionexchange resin.

United States Patent Edward L. Cole Fishklll; Howard V. Hes, Glenham,both of N.Y. 883,339

Dec. 8, 1969 Sept. 21, 1971 Texaco Inc. New York, N.Y.

Inventors Appl. No. Filed Patented Assignee SOIL MICRONUTRIENT PRODUCTField of Search Primary Examiner-Reuben Friedman AssistantExaminer-Richard Barnes AttorneysThomas 1-1. Whaley and Carl G. Riesisms, petroleum catalyst and as a low cost ion-exchange resin.

son. MICRONUTRIENT monuc'r This invention relates to a metal containingpetroleum coke and more particularly to a cationic petroleum cokeprepared by oxidizing a petroleum coke in the presence of water.

Soil for rapidly growing high yield crops may require fertilization orstructural improvement or both depending upon the specific crop or soil.Commercially available inorganic fertilizers generally provide only theso-called primary elements-nitrogen, phosphorus, and potassium, or thesecondary elements-calcium, magnesium, and sulfur. Being watersoluble,such fertilizers are easily leached from the soil; and, they do littleto improve the soil tilth. Furthermore, they must be supplemented withorganic fertilizer and certain trace elements such as copper, iron,manganese, zinc, cobalt, molybdenum, and boron. These trace elements arecalled micronutrients because of the relatively small amounts requiredby plants for healthy growth. Organic fertilizers are necessary as asource of food for energy, growth, and reproduction of soilmicro-organisms.

When a soil is deficient in any micronutrient, crop yields are bound tosuffer. The supply of nutrients in the soil is affected by the parentmaterial from which the soil was derived, along with such things aserosion, leveling, leaching, and removal of trace elements through cropyields. Soil types characterized by micronutrient shortages and inferiorstructure include sand, muck, and peat. Thus for example, 0.04 pound ofcopper, 0.10 pound of zinc, and 0.76 pound of manganese are necessary tosupport the healthy growth of 3,000 pounds of tobacco.

A particular problem associated with the supply of trace elements to thesoil is the necessity to have sufficient capacity for the trace elementswherein such trace elements are released to the soil continuously over aperiod of time. Thus a soil micronutrient which loses the trace elementsthrough for example leaching at an extremely fast rate cannot providethe slow release of nutrients which is needed in order to properlymaintain good crop growth and yields.

it is therefore an object of this invention to provide a micronutrientwhich can provide trace elements to the soil continuously over a longperiod of time.

it is a further object of this invention to provide a cation exchangedcoke which can be produced in good yields and with sufficient cationcapacity to be utilized as a micronutrient.

it has now been found that a micronutrient product which is useful forsupplying trace elements to various crops can be prepared by the processwhich comprises the steps of l) oxidizing a petroleum coke with oxygenin the presence of water and (2) contacting the product from step (1) orthe alkali metal salt thereof with a cation selected from the groupconsisting of copper, iron, magnesium, molybdenum, manganese, zinc,ammonium, cobalt and mixtures thereof. In addition it has beendiscovered that such micrb'nutrient products are capable of preparationby the contacting of the oxidized petroleum coke with a cation as setforth above directly without necessity of prior treatment of theoxidized coke with for example an alkali metal cation. However it iscontemplated within the scope of this invention that the oxidizedpetroleum coke can be converted to the alkali metal salt such as thesodium salt followed by contacting with the various ca tions such ascopper, zinc and iron which are set forth above. In addition theproducts of this invention have excellent exchange capacity and can beproduced in good yields especially when compared to a product which isproduced by the oxidation of petroleum coke by direct oxidation with forexample air in the absence of water. Also, the products of thisinvention resist leaching especially when compared to a petroleum cokewhich has adsorbed thereon various metal cations.

It is contemplated within the scope of this invention that an improvedmethod for supplying trace elements to crops can be accomplished by amethod which comprises contacting a crop with a micronutrient amount ofa product as set forth above. included within such method is thecontacting of a crop with a fertilizer composition comprising afertilizer and a micronutrient amount of the product of this inventionwhich fertilizer compositions have been found to exhibit a reducedtendency to cake.

Thus these new micronutrient fertilizer products of this invention arewater stable and slowly ionize or react in the soil to release traceelements which are vital to plant life. In addition, the products ofthis invention may be used to improve the structure of poor soils suchas soil aggregation, porosity, air permeability, water infiltration, andsoil tilth. Furthermore, the product can help toprevent soil crustingand compaction; and may be used as a plant mulch. As a source of energyfor microbiological activity they can increase the development ofbacteria, fungus, and other micro-organisms in the soil whichmicro-organisms are active in soil processes and are essential tohealthy plant growth. They excrete enzymes that decompose plant residueand organic matter, oxidize ammonia, fix nitrogen, digest protein, andsynthesize new organic compounds. The new micronutrient fertilizers havea marked buffering effect by reducing damage to plant roots fromexcessive acids, alkalis, or salts, In addition, the products of thisinvention are useful as a low cost ion-exchange resin in suchapplications as hydroponics or soilless agriculture.

To prepare the products of the present invention, petroleum coke isoxidized with oxygen in the presence of water to produce an intermediaryproduct (oxidized petroleum coke) or optionally the alkali metalderivative thereof which product is then treated with an aqueoussolution containing the desired cation to form the cation exchangedpetroleum coke. Various cation exchange resins prepared by this processmay be blended to meet the nutrient requirements of a specific crop on aspecific soil, or for pH control. Micronutrient cations are in generalbelieved to be attached to oxidized coke by replacing the 1-! ion in oneor more carboxyl groups or by chelation. In a similar manner, additionalnitrogen may be added to the oxidized coke by treating said oxidizedcoke with a dilute aqueous solution of ammonium hydroxide or ammoniumchloride. Furthermore, a multiion exchange resin may be prepared bytreating a single batch of oxidized petroleum coke in successive stepswith different cation solutions, or in one step with a solutioncontaining mixed cations. By controlling the type and quantity of ionsadded to the oxidized coke, ion exchange resins may be prepared whichwill release in the soil controlled amounts of specific micronutrientsover long periods of time. This prevents high dosages of trace elementswhich might otherwise burn the crop. Furthermore, it has been found thatrain has a reduced tendency to leach these metal coke products from thesoil.

The black body character of cationic petroleum coke increases theabsorptivity of the soil for solar radiation by as much as 40 percent,and makes possible a ground temperature increase of l020 F. Carbon incationic petroleum coke may be utilized by heterotrophic and autotrophicmicro-organisms in the soil as a source of energy for biochemicaltransformations. In addition, the trace elements supplied by thecationic coke favorably influence catalytic efi'ects within the cell,cell membrane structure and permeability, and other phases of thephysiology of bacteria. Heterotrophics include both gram negative andgram positive bacteria as well as spore formers and many fungi andactinomycetes. The two autotrophic genera prominent in soilnitrification are Nitrosomonas and Nitrobacter. The former function asammonia oxidizers and the latter as nitrite oxidizers.

By means of ion exchange reactions in the soil, the cations of metalcoke products can be released for absorption by either micro-organismsor plants during their metabolic processes. The exchangeable cations maypass into the soil through exchange with H-ions from dilute acids formedin the soil by biological processes or introduced as constituents ofrain water or commercial fertilizer. Furthermore, the exchangeablecations may be replaced by other cations already in the soil inaccordance with the lyotropic series which follows in order of replacingpowerz' lithium sodium potassium cesium magnesium calcium strontiumbarium aluminum.

In another theory, it is postulated that the metal coke productsdirectly contacting plant root surfaces exchange coke cations for theI-l-ions which are part of the protein in the plant root. Thus, the cokecations are directly absorbed by the plant root without passing throughan intermediate solution stage.

Petroleum coke is comprised of minute graphitelike crystals imbedded inan organic matrix of highly condensed aromatic compounds such asanthracene, phenanthracene, chrysene, picene and crakene.

The petroleum coke used as a starting material in the process of thisinvention can be produced by the delayed coking" process-a specialprocess for converting heavy residual fuel oil into gasoline, gas oil,and coke. Other petroleum coking processes may be used if they produce apetroleum coke having a similar structure and chemical analysis. In thedelayed coking process, reduced crude oil is charged into the base of afractionating tower. Tower bottoms and a predetermined recycle streamare withdrawn and heated to a temperature of 900-950 F By delayedresidence in a coke drum, the petroleum coke builds up at a temperatureof 850-900 F. and a pressure of 10-100 p.s.i. The petroleum coke is thencooled with water and removed from the delayed coker by hydraulic jet.The coke particles are quite hard and abrasive, and may containsufficient oils to make them tacky. Existing petroleum coke plants varyin size from small units producing 75 tons per day to large multipletower plants producing and handling as much as 1,500 tons per day.Petroleum coke generally has the following composition by weight: fromabout to about 0.5 percent moisture, from about 1 to about 15 percentvolatiles, from about 85 to about 95 percent fixed carbon, from about0.2 to about 1.3 percent ash, and from about 1 to about 5 percentsulfur.

The oxidized coke intermediate is in general prepared by contacting thepetroleum coke with oxygen, including air and activated oxygen,preferably air, in the presence of water including compounds whichgenerate water during the course of the reaction, in general attemperatures of from about 600 F. to about 1,000 P. more preferably fromabout 650 F. to about 850 F., at pressures of from about atmospheric toabout 100 p.s.i.g. more preferably from about atmospheric to aboutp.s.i.g. It is preferred in carrying out the oxidation step to utilizeair wherein the air is saturated with water at a saturation temperatureof from about 50 to about 210 F. more preferably from about 100 to about180 F. In general the concentration of water which is utilized incarrying out the process of this invention is dependent upon the gasrate which is utilized during the oxidation step. Thus concentrations ofwater in the oxygen containing gas is in general from about 0.04 weightpercent to about 70 weight percent more preferably from about 0.05weight percent to about 40 weight percent. The hourly gas rate which isutilized including both air and water that is saturated air is ingeneral from about 0.25 to about 0.75 more preferably from about 0.40 toabout 0.60 based upon the weight of the petroleum coke. The treatingtime will be from 1 to 30 hours and more preferably from 4 to 12 hoursat the above gas rates. In general the yields which are obtained uponoxidation of the petroleum coke are at least about 50 percent morepreferably from about 70 to 90 percent by weight. It is contemplatedwithin the scope of this invention that the oxidation of petroleum cokecan be carried out in the presence of a catalyst such as a vanadiumcatalyst. However it is preferred to carry out such oxidation in theabsence of a catalyst although the use of the term oxidizing a petroleumcoke" includes both the oxidation in the presence and absence of acatalyst.

The exchange capacity of the oxidized petroleum coke expressed asmilliequivalents per gram of oxidized coke is represented by the sum ofthe weak acid and chelating sites.

The number of carboxyl groups in the oxidized coke may be determined bypassing a 1N (CH COO) Ca solution over the oxidized coke followed bytitrating the filtrate with 0.1N KOH solution.

The cation exchange derivative of oxidized petroleum coke may be made bycontacting the coke with the desired cations in an amount sufficient tocombine from about 0.05 to about 5 percent by weight more preferablyfrom about 0.1 to about 2 weight percent and still more preferably fromabout 0.1 to about 1.0 weight percent. In addition the amount of cationincorporated into the oxidized petroleum coke based uponmilliequivalents per hundred grams of product is preferably from about 1to about 150 more preferably from about 5 to about 50. This ispreferably accomplished by shaking washed oxidized petroleum col-re withdilute cationic solutions, e.g. 0.01-5 molar of the desired cations indistilled water for 1 hour to about 16 hours, allowing the mixture tosettle, and then filtering. To prevent unwanted ions in the product, itis preferred to prepare the dilute cationic exchange solutions fromdistilled water. However, pure municipal and natural water of low cationcontent or deionized water may be also used. Treatment with one or moredilute cationic solutions may be necessary to exchange the desiredquantity and type of cations.

The cation exchange may be accomplished in an alternate manner by firstneutralizing the oxidized petroleum coke with the oxides, hydroxides,bicarbonates, or carbonates of an alkali metal, alkaline earth metal, orammonium (for example, sodium or ammonium hydroxide solutions) beforetreating it with the dilute salt solutions of the desired cation. Byneutralizing with ammonium hydroxide, additional nitrogen in the form ofammonia may be added to the oxidized petroleum coke. The resultingammoniated product may be also used for controlling the pH of acidsoils.

The cationic petroleum coke fertilizers of this invention have beenfound not to segregate in storage. They may be uniformly applied to thesoil separately as single cationic cokes, or as blended cationic cokes,or as multicationic cokes. They may be mixed with commercialsuperphosphate fertilizers and drilled into the soil prior to plantingthe seed; or they may be applied as top dressing after the seeds areplanted. In addition, the cationic petroleum coke products wereunexpectedly found to be hydrophilic, permitting them to be sprayed ontothe soil as particulate matter in a water emulsion of petroleum residuaor in a water slurry. Herbicides, antinematode agents and other soilchemicals may be incorporated in such sprays.

The invention can be better appreciated by the following nonlimitingexamples.

EXAMPLE I To a reactor tube (Xi-inch inner diameter by 16 inches inlength) equipped with a diffusion disc at the bottom of said reactortube, gas addition means at the bottom of said tube, exit means at thetop of said tube and heating means is charged 30.5 grams of a delayedcoke from California Crudes (30-60 mesh). The coke is obtained bysolvent extracting a coke having the following properties:

Sulfur, wt. 1.33 Carbon. wt. 7: 95.8 Ash, wt. 0.71 Hydrogen, wt. 4.01Nitrogen, wt. 2.4 Nickel, wt. 0.03 Vanadium, wt. Z; 0.08 Iron, wt. 0.023

with toluene for 18 hours to remove oil soluble components. Thepetroleum coke after extraction is recovered in 99 percent yield andcontains a 1.22 weight percent sulfur and 2.5 weight percent nitrogen.Air which is saturated with water at 100 F. is fed through the bottomgas addition means at a rate of 13.5 liters per hour at a temperature of650 F. The temperature is maintained at 650 F. for a period of 12 hours.The product is reduced in temperature and an oxidized petroleum coke isrecovered at a yield of 59.8 weight percent.

ExAMPLE II To the reactor tube as described in example I is added 30.5

grams of delayed coke from California Crude, the properties I of whichare set forth in Example 1. Air which is saturated with water at atemperature of 100 F. is introduced and continuously added to the cokeat a rate of 13.5 liters per hour over a period of 12 hours whilemaintaining a temperature of 700 F. in the reactor. The temperature isreduced to ambient temperature and an oxidized coke is recovered in ayield'of 55.5 weight percent.

EXAMPLE III to the reactor tube as described in example i is. added 30.5grams of delayed coke fromCalifornia Crude, the properties of which areset forth in Example 1. Air which is saturated with water at atemperature of 100 F. is introduced and continuously added to the cokeat a rate of 13.5 liters per hour over a period of 6 hours whilemaintaining a temperature of 750'F. in the reactor. The temperature isreduced to ambient temperature and an oxidized coke is recovered in ayield of 71 weight percent.

To the reactor tube as described in example I is added 30.5 grams ofdelayed coke from Califoi'i'iia Crude, the properties of which are setforth in Example L'Air which is saturated with water at a temperature of100 F. is introduced and continuously added to the coke at a rate of13.5 liters per hour over a period of 6 hours while maintaining atemperature of 775 F. in the reactor. The temperature is reduced toambient temperature and an oxidized coke is recovered in a yield of 67.8weight percent.

EXAMPLE V To the reactor tube as described in example I is added 30.5grams of delayed coke from California Crude, the properties of which areset forth in example I. Air which is saturated with water at atemperature of 160 F. is introduced and continuously added to the cokeat a rate of 13.5liters per hour over a period of 12 hours whilemaintaining a temperature of 750 F. in the reactor. The temperature isreduced to ambient temperature and an oxidized coke is recovered in ayield of 85.2 weight percent.

EXAMPLE VI To the reactor tube asdescribed in example I is added 30.5grams of delayed coke from California Crude, the properties of which areset forth in examplel. Air which is saturated with water at atemperature of 160 F. is introduced and continuously added to the cokeat a rate of 13.5 liters per hour over a period of 26 hours whilemaintaining a temperature of 750 F.

in the reactor. The temperature is reduced to ambient temperature and anoxidizedcoke is recovered in a yield of 77.2 weight percent.

EXAMPLE VII To the reactor tube as described in example-I is added 30.5grams of delayed coke from California Crude the properties of .which areset forth in example 1. Air ls introduced and continuously added to thecoke at a rate of 13.5 liters per hour over a period of 6 hours whilemaintaining a temperature of 750 F. in the reactor. The temperature isreduced to ambient temperature and an oxidized coke is recovered in ayield of 79.4 percent.

EXAMPLE viii Example V11 is repeated utilizing the same delayed coke asin example 1 except that the temperature in the reactor was maintainedat 850 F. An oxidized coke is recovered in a yield of 53.8 percent.

EXAMPLE IX To the oxidized coke of example I (10 grams) is added anaqueous solution containing 1 percent by weight of zinc chloride. Themixture is shaken for 16 hours and allowed to stand for additionalone-half hour at ambient temperature 1 after which the cation exchangedproduct is recovered by filtration. The filter cake is washed with sixSO-milliliter portions of distilled water and dried on a steam plate.The final wash was free of anion, chloride ion. A cationic petroleumcoke is recovered which contains 0.59 weight percent zinc, 18milliequivalents of zinc per grams of product.

EXAMPLE X In a similar manner as described in example IX the oxidizedcoke of example lis treated with a 1 percent aqueous solution of ferroussulfate heptahydrate. A cationic petroleum cokeis recovered whichcontains 1.03 weight percent iron, 36.9 milliequivalents of iron per 100grams.

EXAMPLE x1 In a similar manneras described in example IX the oxidizedcoke of example I is treated with an aqueous solution containing 1percent manganous sulfate tetrahydrate. A cationic petroleum coke isrecovered which contains 0.09 weight percent manganese, 3.3.milliequivalents manganese per 100 grams product.

EXAMPLE XII In a similar manner as described in example IX the oxidizedcoke of example I is treated with a 1 percent cupric sulfatepentahydrate aqueous solution. A cationic exchanged petroleum coke isrecovered which contains 0.70 weight percent copper, 22 milliequivalentscopper per 100 grams of product.

EXAMPLE XIII In asimilar manner as described in example IX the oxidizedpetroleum coke of example I is contacted with a 0.05 normal sodiumhydroxide solution. A cationic petroleum coke is recovered whichcontains1.53 weight percent sodium, 66.5 milliequivalents of sodium per 100grams of product.

EXAMPLE XIV EXAMPLE XV In a similar manner as described in example IXthe oxidized petroleum coke from example 111 is contacted with a 0.05weight percent aqueous ammonium molybdate solution. A cationic petroleumcoke is recovered which contains 0.036 weight percent molybdenum and aweight percent nitrogen of 4.9.

EXAMPLE XVI In a similar mariner as described in example XV thepetroleum coke of example 111 is treated with a 1 percent by weightaqueous solution of cobaltous sulfate heptahydrate. A cationic petroleumcoke was recovered which contains 0.15 weight percent cobalt, 5.1milliequivalents cobalt. per 100 grams of product. I

EXAMPLE XVII The petroleum coke as set forth in example 1 prior tooxidation is treated with a 1 percent aqueous copper sulfatepentahydrate solution for a period of 3 hours with stirring after whichthe solution is allowed to settle over a 24-hour period at ambienttemperature. The mixture is filtered and the coke is washed with 35parts by weight of water. The washing of the petroleum coke with 35parts of water represents conditions which a micronutrient would besubjected to under actual conditions of rainfall. Thus in general aone-eighth inch of rainfall is equivalent to washing a micronutrientwith 3 times by weight of water. A coke product is recovered whichcontained 0.008 weight percent copper.

EXAMPLE XVIII In the manner of example IX the oxidized coke-s ofexamples VI (presence of water) and VII (absence of water) respective lyare each treated with a 1 percent aqueous copper sulfate pentahydratesolution. The cationic solution after filtration and washing with 300parts of water to 1 part of coke are recovered and the cationicpetroleum coke prepared from the oxidized coke of example VI has a wt.copper of 0.32, 10.1 milliequivalents copper per 100 grams whereas thecationic petroleum coke prepared from the oxidized coke of example VIIhas a weight percent copper of 0.083, 2.7 milliequivalents of copper perhundred grams of product.

EXAMPLE XIX as follows:

("ulionic (like Wetting and (rush wt. Drying ('yclc Strength None No 35None Yes 78 2.5 Yes 34.9 30.0

5 Yes The results set forth in example IX through XIX demon strate theoutstanding properties of the micronutrient products of this invention.More particularly examples XII and XVII demonstrate that a cationicpetroleum coke product of this invention after treatment with fivesuccessive water washes contains 0.70 weight percent copper whereas thesame product of example XVII after washing with 35 parts by weight ofwater contains but 0.008 weight percent. These results demonstrate theability of the products of this invention to resist leaching fromrainfall while providing the necessary slow release of micronutrients tothe soil. In addition example XVIII demonstrates that the products ofthis invention when prepared from a petroleum coke which has beenoxidized with oxygen in the presence of water has greater capacity forexchange of metal than a petroleum coke which is oxidized in the absenceof water. Thus the products of this invention are capable of providingcontinuous release of micronutrients over a longer period of time ascompared to a product prepared by the oxidation of coke in the absenceof water. The results set forth in example XIX clearly demonstrate theanticaking properties which are obtained when the products of thisinvention are blended into various nitrogen containing fertilizers. Moreparticularly the results in example XIX demonstrate that the crushstrength of extruded pellets remains approximately unchanged whensubjected to a wetdry cycle. These results are in sharp contrast to theresults obtained when the fertilizer itself in the absence of theproducts of this invention is subject to a wet-dry cycle. Thus theproducts of this invention provide for continued release ofmicronutrients over a long period of time which products restst leachingand when incorporated with a conventional fertilizer impart anticakingproperties to such fertilizer micronutrient blend.

Obviously, many modifications and variations of the invention, ashereinafter set forth, may be made without departing from the spirit andscope thereof, and therefore, only such limitations should be imposed asare indicated in the appended claims.

We claim:

l. A product prepared by the process which comprises the steps of (l)oxidizing petroleum coke with oxygen in the presence of water and (2)contacting the product from step l or the alkali metal salt thereof witha metal cation selected from the group consisting of copper, iron,magnesium, molybdenum, manganese, zinc, cobalt, ammonium and mixturesthereof.

2. A product of claim 1 wherein the petroleum coke is contacted with airin the oxidation step.

3. A product of claim 2 wherein the water is present in a concentrationof from about 0.05 to about 40 by weight in air.

4. A product of claim 1 wherein the petroleum coke contains from about 0to about 0.5 weight percent moisture from about 1 to about 15 weightpercent volatiles, from about to about weight percent fixed carbon, fromabout 0.2 to about 1.3 weight percent ash and from about 1 to about 5weight percent sulfur.

5. A product of claim 3 wherein the petroleum coke contains from about 0to about 0.5 weight percent moisture from about 1 to about l5 weightpercent volatiles, from about 85 to about 95 weight percent fixedcarbon, from about 0.2 to about 1.3 weight percent ash and from about Ito about 5 weight percent sulfur.

6. A product of claim 1 wherein the cation is present in a concentrationof from about 0.1 to about 2.0 weight percent.

7. A product of claim 2 wherein the cation is present in a concentrationof from about 0.l to about 2.0 weight percent.

8. A product of claim 4 wherein the cation is present in a concentrationof from about 0.1 to about 2.0 weight percent.

9. A product of claim 5 wherein the cation is present in a concentrationof from about 0.1 to about 1.0 weight percent.

10. A method for supporting crop growth in soil which comprisescontacting soil with a micronutrient amount of a product of claim 1.

11. A method for supporting crop growth in soil which comprisescontacting soil with a micronutrient amount of a product of claim 2.

12. A method for supporting crop growth in soil which comprisescontacting soil with a micronutrient amount of a product of claim 4.

13. A method for supporting crop growth in soil which comprisescontacting soil with a micronutrient amount of a product of claim 6.

14. A method for supporting crop growth in soil which comprisescontacting soil with a micronutrient amount of a product of claim 7.

15. A method for supporting crop growth in soil which com- ,prisescontacting soil with a micronutrient amount of a product of claim 9.

2. A product of claim 1 wherein the petroleum coke is contacted with airin the oxidation step.
 3. A product of claim 2 wherein the water ispresent in a concentration of from about 0.05 to about 40 by weight inair.
 4. A product of claim 1 wherein the petroleum coke contains fromabout 0 to about 0.5 weight percent moisture from about 1 to about 15weight percent volatiles, from about 85 to about 95 weight percent fixedcarbon, from about 0.2 to about 1.3 weight percent ash and from about 1to about 5 weight percent sulfur.
 5. A product of claim 3 wherein thepetroleum coke contains from about 0 to about 0.5 weight percentmoisture from about 1 to about 15 weight percent volatiles, from about85 to about 95 weight percent fixed carbon, from about 0.2 to about 1.3weight percent ash and from about 1 to about 5 weight percent sulfur. 6.A product of claim 1 wherein the cation is present in a concentration offrom about 0.1 to about 2.0 weight percent.
 7. A product of claim 2wherein the cation is present in a concentration of from about 0.1 toabout 2.0 weight percent.
 8. A product of claim 4 wherein the cation ispresent in a concentration of from about 0.1 to about 2.0 weightpercent.
 9. A product of claim 5 wherein the cation is present in aconcentration of from about 0.1 to about 1.0 weight percent.
 10. Amethod for supporting crop growth in soil which comprises contactingsoil with a micronutrient amount of a product of claim
 11. A method forsupporting crop growth in soil which comprises contacting soil with amicronutrient amount of a product of claim
 2. 12. A method forsupporting crop growth in soil which comprises contacting soil with amicronutrient amount of a product of claim
 4. 13. A method forsupporting crop growth in soil Which comprises contacting soil with amicronutrient amount of a product of claim
 6. 14. A method forsupporting crop growth in soil which comprises contacting soil with amicronutrient amount of a product of claim
 7. 15. A method forsupporting crop growth in soil which comprises contacting soil with amicronutrient amount of a product of claim 9.